CN111087977A - Inorganic phase-change constant-temperature material and preparation method thereof - Google Patents
Inorganic phase-change constant-temperature material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a phase-change material, in particular to an inorganic phase-change constant-temperature material and a preparation method thereof; the inorganic phase-change constant-temperature material comprises calcium chloride hexahydrate, maleic anhydride, silicon dioxide, sodium carboxymethyl cellulose, acrylic acid, sodium chloride, boric acid and expanded graphite; wherein the total amount of the boric acid and the expanded graphite accounts for 4-12% of the total amount of the inorganic phase change material; the mass ratio of the boric acid to the expanded graphite is 2-6: 2 to 6. The phase change temperature of the inorganic phase change constant temperature material is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is not less than 189KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; it has no deterioration of thermophysical properties during cycling and is not easily leaked from the substrate.
Description
Technical Field
The invention relates to a phase-change material, in particular to an inorganic phase-change constant-temperature material and a preparation method thereof.
Background
In many industries such as food, chemical, low temperature logistics, medical applications, beer, refrigeration, etc., refrigerators are commonly used to maintain a constant temperature at a specific temperature required for environmental or storage. When the refrigerator is powered off, the environment or the specific temperature required for storage cannot be maintained for a long time, so that the temperature rises quickly, the storage time of the articles is short, and the stored articles are easy to deteriorate. In the refrigerating system without phase-change constant-temperature material, when a constant-temperature environment is provided, the refrigerator is frequently started, so that the service life is shortened, and the power consumption is high.
Phase change constant temperature material latent heat cold-storage promptly is the functional material of cold volume of storage in the phase change constant temperature system, and at night power consumption valley period, utilize the material latent heat to store cold volume in phase change constant temperature material, when daytime power consumption peak, release cold volume, satisfy the environment or store the needs. The refrigeration system operates in the night power consumption valley peak period most of the time, and only the auxiliary equipment operates in the daytime power consumption peak period, so that the 'peak shifting and cold consumption, peak shifting and valley filling' of a power grid are realized, and the contradiction between supply and demand of two energy parties is favorably relieved.
At present, the research on low-temperature phase change cold storage materials is less, but the constant-temperature materials are in great demand in various industries such as food, chemical industry, low-temperature logistics, medical application, beer, refrigeration and the like. Therefore, the research on the low-temperature phase-change constant-temperature material is especially important for developing a novel low-temperature phase-change constant-temperature material which has the advantages of 17 ℃ of phase-change temperature, large phase-change latent heat, small supercooling degree, no phase separation and stable performance.
CN103374334A discloses an inorganic phase change material (PCM-17) with a phase change temperature of 17 ℃, comprising 28.5% by mass of calcium chloride hexahydrate, 4.5% by mass of maleic anhydride, 4.8% by mass of silicon dioxide, 5.6% by mass of sodium carboxymethylcellulose, 6% by mass of acrylic acid, 2.6% by mass of sodium chloride and 48% by mass of water; however, the phase change material disclosed in the patent application has a problem that the thermophysical properties are easily degraded during the cycle and the phase change material is easily leaked from the matrix.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an inorganic phase-change constant-temperature material; the inorganic phase-change constant-temperature material is not easy to cause the problem of thermophysical property degradation in the circulating process and is not easy to leak from a matrix.
Specifically, the inorganic phase-change constant-temperature material comprises calcium chloride hexahydrate, maleic anhydride, silicon dioxide, sodium carboxymethyl cellulose, acrylic acid, sodium chloride, boric acid and expanded graphite;
wherein the total amount of the boric acid and the expanded graphite accounts for 4-12% of the total amount of the inorganic phase change material; the mass ratio of the boric acid to the expanded graphite is 2-6: 2 to 6.
The invention discovers that the problem of thermophysical property degradation of the phase-change material in the circulation process can be avoided by mixing boric acid and expanded graphite into the existing phase-change material, and the phase-change material can be prevented from leaking from a matrix.
Preferably, the inorganic phase-change constant-temperature material comprises the following components in parts by weight:
preferably, the inorganic phase-change constant-temperature material comprises the following components in parts by weight:
as a better technical scheme of the invention, the inorganic phase-change constant-temperature material comprises the following components in parts by weight:
the invention also provides a preparation method of the inorganic phase-change constant-temperature material, which comprises the following steps:
(1) mixing sodium carboxymethylcellulose with 8-10% of water, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 16-20% of water, and carrying out chemical reaction to obtain a mixed solution II;
(3) mixing acrylic acid with 8-10% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing boric acid, expanded graphite, the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and carrying out chemical reaction to obtain a high polymer material;
(5) mixing the polymer material with the remaining part of water.
The phase change temperature of the inorganic phase change constant temperature material prepared by the method is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is not less than 189KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; meanwhile, the boric acid and the expanded graphite are introduced, so that the problem that the thermophysical properties of the graphite are easy to degrade and the problem that the graphite is easy to leak from a matrix in the circulating process are solved.
In addition, the preparation method of the invention adds four parts of water.
Preferably, the chemical reaction in the step (2) is carried out at 30-40 ℃ for 0.8-1.2 h.
Preferably, the chemical reaction in the step (4) is carried out at 35-45 ℃ for 0.5-1.5 h.
The invention has the beneficial effects that:
(1) the phase change temperature of the inorganic phase change constant temperature material is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is not less than 189KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000;
(2) the inorganic phase-change constant-temperature material does not have the condition of thermophysical property degradation in the circulating process, and is not easy to leak from a matrix;
(3) the inorganic phase-change constant-temperature material has stable performance, no toxicity, no corrosion and good plasticity;
(4) the preparation method has simple and convenient process flow and is easy for mass production.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides an inorganic phase-change constant-temperature material which comprises the following components in parts by weight:
the preparation method of the inorganic phase-change constant-temperature material comprises the following steps:
(1) mixing sodium carboxymethylcellulose with 10% water at 25-35 ℃, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 18% of water, and reacting for 1h at 40 ℃; to obtain a mixed solution II
(3) Mixing acrylic acid with 9% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing boric acid, expanded graphite, the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and reacting at 40 ℃ for 1h under normal pressure to obtain a high polymer material;
(5) and mixing the high polymer material with the rest part of water, and standing for 10-15 min to obtain the water-based paint.
The phase change temperature of the inorganic phase change constant temperature material obtained in the embodiment is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is 189KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; and there is no deterioration of thermophysical properties during the cycle and leakage from the matrix is not easy.
Example 2
The embodiment provides an inorganic phase-change constant-temperature material which comprises the following components in parts by weight:
the preparation method of the inorganic phase-change constant-temperature material comprises the following steps:
(1) mixing sodium carboxymethylcellulose with 9% of water at 25-35 ℃, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 17% of water, and reacting for 1h at 40 ℃ to obtain mixed solution II;
(3) mixing acrylic acid with 8% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing boric acid, expanded graphite, the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and reacting at 40 ℃ for 1h under normal pressure to obtain a high polymer material;
(5) and mixing the high polymer material with the rest part of water, and standing for 10-15 min to obtain the water-based paint.
The phase change temperature of the inorganic phase change constant temperature material obtained in the embodiment is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is 192KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; and there is no deterioration of thermophysical properties during the cycle and leakage from the matrix is not easy.
Example 3
The embodiment provides an inorganic phase-change constant-temperature material which comprises the following components in parts by weight:
the preparation method of the inorganic phase-change constant-temperature material comprises the following steps:
(1) mixing sodium carboxymethylcellulose with 8% of water at 25-35 ℃, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 20% of water, and reacting for 1h at 40 ℃ to obtain mixed solution II;
(3) mixing acrylic acid with 8% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing boric acid, expanded graphite, the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and reacting at 40 ℃ for 1h under normal pressure to obtain a high polymer material;
(5) and mixing the high polymer material with the rest part of water, and standing for 10-15 min to obtain the water-based paint.
The phase change temperature of the inorganic phase change constant temperature material obtained in the embodiment is 17 ℃, the supercooling degree is 0.3 ℃, the phase change latent heat is 190KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; and there is no deterioration of thermophysical properties during the cycle and leakage from the matrix is not easy.
Comparative example 1
The comparative example provides an inorganic phase-change constant-temperature material which comprises the following components in parts by weight:
the preparation method of the inorganic phase-change constant-temperature material comprises the following steps:
(1) mixing sodium carboxymethylcellulose with 9% of water at 25-35 ℃, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 18% of water, and reacting for 1h at 40 ℃ to obtain mixed solution II;
(3) mixing acrylic acid with 9% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and reacting at 40 ℃ for 1h under normal pressure to obtain a high polymer material;
(5) and mixing the high polymer material with the rest part of water, and standing for 10-15 min to obtain the water-based paint.
The phase change temperature of the inorganic phase change constant temperature material obtained by the comparative example is 17 ℃, the supercooling degree is 0.5 ℃, the phase change latent heat is 172KJ/Kg, the phase change process is reversible, and the number of times of recycling is not less than 10000; but the phenomenon of deterioration of thermophysical properties occurs during the cycle and leakage from the matrix is easy.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. An inorganic phase-change constant-temperature material is characterized by comprising calcium chloride hexahydrate, maleic anhydride, silicon dioxide, sodium carboxymethylcellulose, acrylic acid, sodium chloride, boric acid and expanded graphite;
wherein the total amount of the boric acid and the expanded graphite accounts for 4-12% of the total amount of the inorganic phase change material; the mass ratio of the boric acid to the expanded graphite is 2-6: 2 to 6.
2. The inorganic phase-change thermostatic material as claimed in claim 1, which is characterized by comprising the following components in parts by weight:
3. the inorganic phase-change thermostatic material as claimed in claim 1 or 2, characterized by comprising the following components in parts by weight:
4. the inorganic phase-change thermostatic material as claimed in any one of claims 1 to 3, characterized by comprising the following components in parts by weight:
5. the preparation method of the inorganic phase-change constant-temperature material as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) mixing sodium carboxymethylcellulose with 8-10% of water, and adding maleic anhydride to obtain a mixed solution I;
(2) adding silicon dioxide into the mixed solution I, then adding 16-20% of water, and carrying out chemical reaction to obtain a mixed solution II;
(3) mixing acrylic acid with 8-10% of water, and adding sodium chloride to obtain a mixed solution III;
(4) mixing boric acid, expanded graphite, the mixed solution II and the mixed solution III, adding calcium chloride hexahydrate, and carrying out chemical reaction to obtain a high polymer material;
(5) mixing the polymer material with the remaining part of water.
6. The method according to claim 5, wherein the chemical reaction in step (2) is carried out at 30-40 ℃ for 0.8-1.2 h.
7. The method according to claim 5 or 6, wherein the chemical reaction in step (4) is carried out at 35-45 ℃ for 0.5-1.5 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480877A (en) * | 2020-12-24 | 2021-03-12 | 西北大学 | Calcium chloride dihydrate composite greenhouse phase change heat storage material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484074A (en) * | 2012-06-15 | 2014-01-01 | 中瑞森(天津)新能源科技有限公司 | Inorganic phase transition material having phase transition temperature of 15DEG C |
| CN108251065A (en) * | 2018-01-11 | 2018-07-06 | 青海大学 | A kind of low-temperature inorganic hydrous salt phase transition energy-storing material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484074A (en) * | 2012-06-15 | 2014-01-01 | 中瑞森(天津)新能源科技有限公司 | Inorganic phase transition material having phase transition temperature of 15DEG C |
| CN108251065A (en) * | 2018-01-11 | 2018-07-06 | 青海大学 | A kind of low-temperature inorganic hydrous salt phase transition energy-storing material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480877A (en) * | 2020-12-24 | 2021-03-12 | 西北大学 | Calcium chloride dihydrate composite greenhouse phase change heat storage material |
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Application publication date: 20200501 |